Production of aromatics



' May 14, 1946. M, C K, JQNES ETAL 2,400,355

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Patented May 14, 1946 Y UNITED a STATES PATENT OFFICE yMinorCJi. Jones, Mountainside, and Frederick f W, Schwachen-Westfield N. J., assignorstoV Standard Oil Development Comparini; corporation of Delaware I Applicationoctober14, 1942, kSerial N:.'.i`61,91772` v 4`c1aims.," ci. 26o-6701l b i v Y presencepf oleiinic hydrocarbons, in order toV Thefpresent invention relates to improvements in the art of` producing aromatichydrocarbons from petroleum oil sources' and, more particu larlyz it relates -to`y improvements in 'the artof solvent treating` petroleum fractions containing aromatics'under such' conditions as'to avoid -loss of phenolic solvents which are customarily empioyed as selective solvents inthe recovery of the aromatics. Y j l Recently, a great deal of research has been directed toward the 'production of 'aromatica particularly toluene from petroleum oil sources. There are several methods of producing toluene,

as follows: In the firstplace, toluene occurs naturally in relatively small amounts in virgin oil. In the second place, toluene isv produced in the catalytic cracking,-forgexample, of gas oil. Thirdly, toluene may be produced by steam cracking a gas oil. Again, there is also another im# portant process for producingV toluene-which involves the dehydrogenation of C1 hydrocarbons such as vn'iethylcycloherrane Vin. thefpre'sence of' a catalyst. This latter operation generallyis recrackingof gas oil, the operationis usually performed under such' conditions that -therefare produced substantial quantities of cleflns, and the sameis true with respect to catalyticcracking. f

` In the usual process of recovering toluene from the oil, a relatively narrow boiling cut, say boiling from 195 F.-250 F., is segregated and,accord ing to best procedure, thisffraction,isjvaporized and treated with liqefiedanhydrous phenol in av solvent extraction zone', vwhereuponthe vtoluene which is concentrate'din the'vapor fraction is dissolved in the phenol andthereafter'recovered t therefrom by fractional distillation.' Except in'.-

the case where thetoluene is extracted from virminimize the amount of solvent lost in the process and to 'avoid the formation lof high-boiling non- ,phenolic material in the solvent.

* converting it into nonusable reaction products-.

K fraction produced by cracking gas oil in the presf ferred to ascatalytic reforming. In-the steam* In the accompanying drawing; we have shown by means of a iiowv planl a preferred modification of operating our invention. I

. Referring in detail tothe drawing, a, naphtha ence of 75 mol. of steam V (in which operation thercracking'furnace was atan inlet pressure of` `63.5 lbs. gauge and anv outlet pressure ofY 17.5 lbs.v

-. mentv with clay at 1` at a. temperature within the range of fromabove 300 SE1-343? F..while xnain.y taining a ypressure of about 100-lbs. p er square inch gauge o n -f the system and ata' feedrate of about 0.*25'volumev of oil -per Vvolume ofvcatalyst u per-hour, whereupon the olensand particularly. the conjugated kdiolefins were polymerized and withdrawn as heavypolymer as indicated in the drawing. The` charging stock substantially freeV of `its conjugated diA-oletlnic content` was then f fractionated at`3 .and a narrow boiling fraction comprising about 21 vvolume Ypercent of the origilosses. v'In particular, the `dioleflnic hydrocarbons.

which are present polymerize-to form high' boil ing non-.phenolic materialin1thesolvent which as well as toexcesleads to `operating difficulties Itfis the main lobject of our invention tocon- `dition'.hydrocarbons containing aromatics to beL solvent treated in order to improve the latter operation and render it operablegtechnicallykand economically. a l v.

y A more specific object of tour present invention is to make possible the recovery of toluene from hydrocarbons containing this, aromatic` in the nal material (containing 21%,.toluene) andbo'ilinglwithinv the range of from 175 F.265,F. was withdrawn and again treated at 5 with clay. at a temperature within the rangel of from about400". f

FTQ-515 F.- while maintaining a pressure of about, .lbs.'per square inch gauge 'onthe system and feeding the fraction to the clay treatmenttat ,a

raterof about 1 volume 'of oil per volume of catalyst per hour.Av It will be noted that -in'this second clay treatment the. temperatures were somewhat higher as was the feed'rate.

Thisfsecond clay treatment resulted in theffurther formationjof-.heavy polymer and this `gvas withdrawn from the system as'indicated, leaving a residue amounting to 19% by volume of the original naphtha, which was then subjected after suitable heating to further fractionation at 10.

In carrying out the fractionation at 10, we employed'a 100 plate fractionation column and from this fractionation we recovered a fraction boiling within the range from 200 F.-2'40 F. (containing 38 toluene) representing 11.5% of the original naphtha charged to the system and this fraction was then subjected at l2to a vapor-liquid extraction treatment, that is to say, the hydrocarbons in vapor form were treated with liquid phenol at a temperature at the top of the column of about 220 F. and at the bottom of the column of about 330 F., the ratio of liquefied phenol by weight to the feed hydrocarbons being VIi to 1. and in which solvent treatment we employed a reflux ratio of 1 to 1; that is to say, we recycled to the solvent treating zone a weight of hydrocarbon overhead equal to the weight of the nonaromatic portion withdrawn from the treating zone. The details of vapor-liquid extract treatment are well-known and need not be discussed at length here. The application of Chester'lr Read, Serial No. 394,983, filed May 24, 1941, gives a full description of this type of operation.

The solvent treatment resulted, of course, in the formation of'two phases, namely a raffinate phase which was withdrawn as indicated from 12, and an 'extract phase (containing 96% toluene) representing 4.2 volume percent of the original naphtha, and this extract phase after liberation of the solvent therefrom was subjected to treatment with sulfuric acid of 98% strength, 25 lbs. of the said acid being employed for each barrel of oil, this operation taking place at v14 in the drawing. After washing, neutralizing and distilling in a finishing still according to known methods, nitration grade toluene, that is, toluene of 99+% purity, was obtained in an amount equal to 4%y by volume of the original naphtha charged to the system. The effectiveness of the process is shown by the fact that this `nitrationy grade toluene was 89% of the toluene originally present in the naphtha.

It has already been pointed out that when vapor-liquid extracting cracked naphthas, such as the steam cracked naphtha rst discussed, for recovery of aromatics such as toluene, appreciable reaction took place between fthe naphtha and phenol used as solvent, even though the original naphtha had beenl clay treated for removal of olenic type constituents. In addition, high boiling non-phenolic material was produced which accumulated in the solvent. Both of these fac,- tors led to operating diillculties aswell as exces-j sive solvent losses.

In the example now under discussion, vthe phenol Vremaining in the extraction system after approximately 20 volumes of naphtha'per volume a similar trial of phenol extraction of virgin naphtha and analysis of the phenol, r2% of residue remained after removal of pure phenol, and the phenol content of the last 5% fraction of the analytical distillation was 98%. Thus, the present inyention has made possible on cracked naphtha results approximately equivalent to Vthose obtained with virgin naphthas, and has made possible recovery of toluene from cracked naphthas that are particularlyy rich in aromatics and other than for `the presence of oleflnic material, highly desirable sources of toluene.- 1

While particularly applicable to conditioning feed stock for vapor-liquid extraction with phenol, Vthe present process may be used to condition feed to any of the successful processes for extraction of aromatics, such as sulfur dioxide extraction, and extraction with alkylated phenols and other solvents.

of phenol had been extracted was analyzed by distillation after removal of all naphtha. When `pure phenol was 30%, and the last 5% fraction from the analytical distillation contained '55% phenol. l Thus, the process as set forth in this invention saved over 27% of the phenol used. In

However, when all of the steps It will be distinctly understood that in the foregoing specific example which wehave given, set ting forth theresults of arun which we made, the specific details are merely illustrative and domot impose any limitation on our4 invention. Thus,

for example, the Vclay treatment carried out at 1.

may be successfully .operated under the following range of conditions:

Temperature, 11k-400" F. Pressure, atmospheric to 400# Feed rate, 0.25-1.0 v./v./hr.

'I o recapitulate, our present invention relates to improvements in the recovery of toluene and other aromatics from a hydrocarbon mixture containing, in addition to the desired aromatic such as toluene, appreciable quantities of olefins and particularly conjugated diolens. Y If such a product is treated in vapor phase with liquefied phenol, we have found that some sort of reaction takes place betweenk the phenol and the olefins, and while wedo not wish to be bound by any theory, we believe that the 4phenols are alkylated and that the olefins are polymerized to form a high boilingpolymer-which, because'of its high boiling point, is morev readily separated from the phenol by distillation and serves to dilute the phenol thus introducing a multiplicity of operating difiiculties and of course causing a loss of phenol. Or, the phenols may react by condensation with the olens tofform resins.l To correct this. diillculty ins solvent treating process, we have devised the present process of clay treating the hydrocarbon mixture containing' the desired aromatic to polymerize and remove the olefins prior to the solvent treatment. For this clay treatment we may use any known polymerizing clay such as fullers earth, activated bentonites, etc. which are available under such trade names as Attapulgus clay, Floridln, Milwhite and. Superfiltrol. Also, instead yof using two stages of clay treatment, we may employ a single stage or we may employ several stages of clay treatment.; i i

Numerous modifications of our invention falling within the spirit thereof will readily suggest themselves to those who are familiar with this art. What we claim is: l. Process for manufacturing toluene, which Y asoman comprises subjecting a naphtha fraction tol treat-k Y ment with clay at elevated temperature while imposing superatmospherlc pressure thereon, whereby the olens present are at least partly .po1ymerized, separating the polymerized prodf ucts', fractionating the remainder of Vthe clay Vtreated product to recover a fraction boiling substantially within the lrange of fromr1'?5y F. to

about 265 F., subjecting the -said fraction to a second clay treatmentv at higher temperature than employed in the flrstclay 'treatment wherevent treatment -to form an extract containing toluene, separating the toluene from the solvent and recovering the said soiuene. f ,Y

2. The method set forth in claim 1 in which the temperatureV employed in the flrst clay treating step is from about 310F. to about 343 F. t

3. The methodset forth in claim 1, in which the temperature employed in the secondvclay treating step is from about 400 F, to about 515 il'.l

4. In the process of purifying toluene contain-v ing .fractions to recover. toluene ofV nitratable grade, the improvement which .comprises .sub

jecting the4 crude tolueneY toa clay treatment `at elevated temperature and pressure torpolymerize at least a portion of the olens present, separat'- ing the polymer, fractionating theproduct remaining after the polymer separation, subject-- ing a fraction containing toluene to a vsecond clay treatment ,at a higherA temperature than that employed inthe rst v stage and also elevated pressure to polymerize; olefins,` separating the polymer, subjecting the .produ'ct remaining after the second polymer removal to a second t fractionation to recover a toluene fraction, thereafter recovering toluene by treating with a phenolic solvent to form an extract of toluene, separating the toluene from the solvent, acid treat.

ing the separated toluene and thereafter recovf ering toluene of nitratable grade.

MINOR c. K. JONES. FREDERICK W. SCHUMACHER. 

